Dissipative Equation of Motion for Electromagnetic Radiation in Quantum Dynamics

BUSTAMANTE, CARLOS M.; GADEA, ESTEBAN D.; HORSFIELD, ANDREW; TCHAVDAR TODOROV; GONZÁLEZ LEBRERO, MARIANO C.; DAMIAN A. SCHERLIS

PHYSICAL REVIEW LETTERS

AMER PHYSICAL SOC

Lugar: New York; Año: 2021 vol. 126 p. 87401 - 87401

0031-9007

The dynamical description of the radiative decay of an electronically excited state in realistic many-particle systems is an unresolved challenge. In the present investigation electromagnetic radiation of the charge density is approximated as the power dissipated by a classical dipole, to cast the emission in closed form as a unitary single-electron theory. This results in a formalism of unprecedented efficiency, critical for ab initio modeling, which exhibits at the same time remarkable properties: it quantitatively predicts decay rates, natural broadening, and absorption intensities. Exquisitely accurate excitation lifetimes are obtained from time-dependent DFT simulations for C2+, B+, and Be, of 0.565, 0.831, and 1.97 ns, respectively, in accord with experimental values of 0.57±0.02, 0.86±0.07, and 1.77?2.5 ns. Hence, the present development expands the frontiers of quantum dynamics, bringing within reach first-principles simulations of a wealth of photophysical phenomena, from fluorescence to time-resolved spectroscopies.